Semiconductor device and its manufacture method

ABSTRACT

(a1) A concave portion is formed in an interlayer insulating film formed on a semiconductor substrate. (a2) A first film of Mn is formed by CVD, the first film covering the inner surface of the concave portion and the upper surface of the insulating film. (a3) Conductive material essentially consisting of Cu is deposited on the first film to embed the conductive material in the concave portion. (a4) The semiconductor substrate is annealed. During the period until a barrier layer is formed having also a function of improving tight adhesion, it is possible to ensure sufficient tight adhesion of wiring members and prevent peel-off of the wiring members.

CROSS REFERENCE TO RELATED APPLICATION

This application is based on and claims priority of JP2005-250046 filedon Aug. 30, 2005, the entire contents of which are incorporated hereinby reference.

BACKGROUND OF THE INVENTION

A) Field of the Invention

The present invention relates to a semiconductor device manufacturemethod, and more particularly to a semiconductor device manufacturemethod suitable for forming wirings by a damascene method by which aconcave portion formed in an interlayer insulating film is filled with aconductive member.

B) Description of the Related Art

Miniaturization of wirings and increasing of wiring layers areprogressing as semiconductor elements are highly integrated and chipsizes are reduced. In a logical element having a multi-layer wiringstructure, a delay of a signal transmitting along a wiring is becoming adominant factor of lowering an operation speed of the logical element.The delay of a signal transmitting along a wiring is proportional to aproduct of a wiring resistance and a parasitic capacitance betweenwirings.

Technologies of using copper (Cu) having a low resistivity as wiringmaterial are adopted practically in order to reduce wiring resistance.Since it is difficult to pattern a copper film by using photolithographyprocess, a damascene method is generally adopted to form copper wirings.

When a copper wiring is formed by the damascene method, the innersurface of a wiring trench and a via hole is covered with a barrierlayer before the copper film is deposited, the main object of thebarrier layer being to prevent diffusion of copper into an insulatingfilm. Refractory metal such as tantalum (Ta) and tungsten (W) is used asthe material of a barrier film. Refractory metal has a resistivityhigher than that of copper.

As the size of a wiring becomes fine, a ratio of the barrier layeroccupying the cross section of the wiring becomes large. Therefore, thebarrier layer has a large factor of raising a wiring resistance.Especially, in a fine multi-layer wiring structure having a diameter andwiring width of a via hole of 0.1 μm or smaller, it is desired to makethe barrier layer as thin as possible.

The document “Low-temperature passivation of copper by doping with Al orMg” by W. A. Lanford et al., Thin Solid Films, 262 (1995), pp. 234 to241 discloses the technique of forming an Al oxide or Mg oxide layer onthe surface of Cu by doping Al or Mg into Cu and performing heattreatment. This oxide layer functions as a protective film and diffusionpreventing film for Cu.

Next, description will be made on a method of forming a thin barrierlayer having a uniform thickness, disclosed in the document “LowResistive and Highly Reliable Cu Dual-Damascene Interconnect TechnologyUsing Self-Formed MnSi_(x)O_(y) Barrier layer” by T. Usui et al., IITC2005, Session 9.2. A seed layer of CuMn alloy is formed by sputtering onthe surface of an interlayer insulating film formed with wiring trenchesand via holes. Thereafter, copper is electroplated to fill the wiringgroove and via hole with the copper. Heat treatment is performed toreact Si and O as the constituent elements in the interlayer insulatingfilm with Mn as the constituent element in the seed layer. A barrierlayer is therefore formed at the interface between a Cu wiring and theinterlayer insulating film, the barrier layer being made ofMnSi_(x)O_(y) compound which is very thin about 2 to 3 nm in thicknessand has a uniform thickness. This barrier layer prevents diffusion ofCu.

The seed layer covering the bottom of the via hole does not contact theinterlayer insulating film and contacts a lower level wiring. Therefore,the barrier layer is not formed at the interface between the copperwiring in the via hole and the lower level wiring, so that the upper andlower level wirings can be connected without the barrier layer betweenthe upper and lower level wirings. Further, since the barrier layer madeof MnSiO compound can be made thinner than a barrier layer made ofrefractory metal, it is possible to suppress an increase of wiringresistance.

SUMMARY OF THE INVENTION

In a conventional method of forming a barrier layer made of MnSiOcompound at an interface between a copper wiring and an interlayerinsulating film, the barrier layer has also a function of enhancingtight adhesion of the copper wiring. The barrier layer made of MnSiOcompound is not formed during the period after the seed layer of CuMnalloy is formed and before heat treatment is executed. The presentinventors have found that sufficient tight adhesion is not obtainedbetween the seed layer and interlayer insulating film in such a statewhere the barrier layer is not formed. More specifically, a copperwiring may be peeled off after copper is electroplated and before heattreatment is executed.

Tight adhesion was evaluated by forming 25 samples which have CuMn alloylayers having a thickness of 90 nm formed on a surface of each ofsilicon oxide films, porous methylsilsesquioxane (porous MSQ) films,SiCN films and SiOC films. Tape tests were conducted and peel-off arosein all samples. Tape tests were conducted after heat treatment for oneminute at 300° C. in a nitrogen atmosphere, and peel-off did not arisein any samples. This may be ascribed to improved tight adhesion becauseheat treatment forms a barrier layer of MnSiO compound. It can beunderstood from this that the state before heat treatment does notensure sufficient tight adhesion.

It is expected that a copper wiring can be prevented from being peeledoff, if heat treatment is executed to form a barrier layer of MnSiOcompound before copper electroplating is performed. However, heattreatment is executed before copper electroplating, the seed layer ofCuMn alloy is aggregated and it becomes difficult to fill a wiringtrench and a via hole with copper at good reproductivity.

An object of the present invention is to provide a semiconductor devicemanufacture method capable of obtaining sufficient tight adhesion ofwiring material and preventing peel-off of the wiring material before abarrier layer having also a function of improving tight adhesion isformed. Another object of the present invention is to provide asemiconductor device suitable for being manufactured by this method.

According to one aspect of the present invention, there is provided asemiconductor device manufacture method comprising steps of: (a1)forming a concave portion in an interlayer insulating film formed on asemiconductor substrate; (a2) forming a first film of Mn by CVD, thefirst film covering an inner surface of the concave portion and an uppersurface of the insulating film; (a3) depositing conductive materialessentially consisting of Cu on the first film to embed the conductivematerial in the concave portion; and (a4) annealing the semiconductorsubstrate.

According to another aspect of the present invention, there is provideda semiconductor device manufacture method comprising steps of: (b1)forming a concave portion in an interlayer insulating film formed on asemiconductor substrate; (b2) forming a first film containing Cu and Mnby CVD, the first film covering an inner surface of the concave portionand an upper surface of the insulating film; (b3) depositing conductivematerial essentially consisting of Cu on the first film to embed theconductive material in the concave portion; and (b4) annealing thesemiconductor substrate.

According to another aspect of the present invention, there is provideda semiconductor device manufacture method comprising steps of: (c1)forming a concave portion in an interlayer insulating film formed on asemiconductor substrate; (c2) forming a first film containing Cu and Mnby sputtering, the first film covering an inner surface of the concaveportion and an upper surface of the insulating film; (c3) forming asecond film of conductive material essentially consisting of Cu by CVDon the first film; and (c4) embedding conductive material essentiallyconsisting of Cu in the concave portion.

According to another aspect of the present invention, there is provideda semiconductor device manufacture method of depositing alloy containingCu and Mn on a semiconductor substrate by CVD while Mn source materialand Cu source material are supplied at the same time.

Sufficient adhesion can be ensured by forming the first film by CVD inthe step (a2) or (b2). If the first film is formed by sputtering in thestep (c2), tight adhesion can be ensured while the second film is formedby CVD in the step (c2).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional view of a semiconductor device manufacturedby a semiconductor device manufacture method according to an embodiment.

FIG. 2 is a table showing materials of an underlying film and aconductive member and film forming methods adopted by semiconductordevice manufacture methods according to the first to ninth embodiments.

FIGS. 3A to 3F are cross sectional views of a device during manufacture,illustrating the semiconductor device manufacture method according tothe first embodiment.

FIG. 4 is a schematic diagram showing a CVD system to be used by thesemiconductor device manufacture methods of the embodiments.

FIGS. 5A to 5C are cross sectional views of a device during manufacture,illustrating the semiconductor device manufacture method according tothe fifth embodiment.

FIGS. 6A to 6C are cross sectional views of a device during manufacture,illustrating the semiconductor device manufacture method according tothe seventh embodiment.

FIGS. 7A and 7B are cross sectional views of a device duringmanufacture, illustrating the semiconductor device manufacture methodaccording to the ninth embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIG. 1 is a schematic cross sectional view of a semiconductor devicemanufactured by an embodiment method. An element isolation insulatingfilm 2 is formed in a surface layer of a semiconductor substrate 1 byshallow trench isolation (STI) to define a plurality of active regions.A MOS transistor 3 is formed in an active region. The MOS transistor 3is constituted of a source region 3S, a drain region 3D, a gateinsulating film 31 and a gate electrode 3G.

An interlayer insulating film 4 of silicon oxide having a thickness of300 nm and a protective film 6 of SiOC having a thickness of 50 nm areformed on the semiconductor substrate 1, covering the MOS transistor 3.A via hole is formed through the protective film 6 and interlayerinsulating film 4, to expose a partial surface of the drain region 3D onthe bottom of the via hole. A conductive plug 5B of tungsten (W) isembedded in the via hole. A barrier metal layer 5A of TiN having athickness of 25 nm is disposed between the conductive plug 5B and theinner surface of the via hole.

The structure described above can be formed by well-knownphotolithography, etching, chemical vapor deposition (CVD), chemicalmechanical polishing (CMP) and the like.

An interlayer insulating film 10 made of low dielectric constantinsulating material is formed on the protective film 6. A wiring trenchis formed in the interlayer insulating film 10, reaching the bottom ofthe film 10 and crossing over the conductive plug 5B. A first layercopper wiring 11 is embedded in the wiring trench. The copper wiring 11is connected to the conductive plug 5B.

A cap film 20, a via interlayer insulating film 21, an etching stopperfilm 22 and a wiring interlayer insulating film 23 are formed on theinterlayer insulating film 10 in this order recited.

A wiring trench 25 is formed in the wiring interlayer insulating film23, and a via hole 24 is formed in the via interlayer insulating film21. The wiring trench 25 reaches the upper surface of the etchingstopper film 22. The via hole 24 opens on the bottom of the wiringtrench 25 and reaches the upper surface of the lower level wiring 11through the cap film 20.

A conductive member 30 of copper or copper alloy is embedded in thewiring trench 25 and via hole 24. The conductive member 30 is connectedto the first layer wiring 11 to constitute a second layer wiring. Thedetailed structure including the barrier layer will be later describedin each of the embodiments.

A cap film 50, a via interlayer insulating film 51, an etching stopperfilm 52 and a wiring interlayer insulating film 53 are stacked on thewiring interlayer insulating film 23. Similar to the second level wiringstructure, a wiring trench 55 and a via hole 54 are formed and aconductive member 60 is deposited therein. The conductive member 60constitutes a third layer wiring.

Next, description will be made on the first to ninth embodimentscharacterized in the methods of forming the first layer wiring 11,second layer conductive member 30 and third layer conductive member 60.

FIG. 2 shows a list of materials and deposition methods of an underlyingfilm and a conductive member when a wiring or conductive member isformed by the methods of the first to ninth embodiments. “CVD”,“SPUTTER” and “EP” described to the left of hyphens in the list meanfilm formation by a CVD method, a sputtering method and anelectroplating method, respectively. “Mn”, “Cu” and “CuMn” described tothe right of hyphens in the list mean that the materials of depositedfilms are Mn, Cu and CuMn alloy, respectively.

With reference to FIGS. 3A to 3F, description will be made on asemiconductor device manufacture method according to the firstembodiment. In the following description, attention is paid to a methodof forming the second layer wiring structure from the cap layer 20 tointerlayer insulating film 23. The second layer wiring structure isformed by a dual damascene method. The third layer wiring structure isformed by the same method as that used for the second layer wiringstructure. The first layer wiring 11 is formed by a single damascenemethod, and a barrier layer forming method, a method of depositing aconductive member in the wiring trench are the same as those adopted inthe method of forming the second layer wiring structure.

As shown in FIG. 3A, a cap film 20, a via interlayer insulating film 21,an etching stopper film 22 and a wiring interlayer insulating film 23are sequentially formed on an interlayer insulating film 10. Forexample, the cap film 20 has a two-layer structure of a silicon oxide(SiO) film and a silicon carbide (SiC) film, and has a total thicknessof 20 to 70 nm. For example, the etching stopper film 22 is made of SiCor silicon nitride (SiN) and has a thickness of 20 to 70 nm. These filmscan be formed by CVD.

The interlayer insulating films 21 and 23 are made of organic orinorganic low dielectric constant insulating material and have athickness of 300 to 700 nm. The inorganic low dielectric constantinsulating material may be porous silica or SiOC. The organic lowdielectric constant insulating material may be SiLK (registeredtrademark) manufactured by the Dow Chemical Company. These materialscontain Si and O as the constituent elements.

As shown in FIG. 3B, a wiring trench 25 is formed through the wiringinterlayer insulating film 23, and a via hole 24 is formed through thevia interlayer insulating film 21. For example, the size of the via hole24 in a plan cross section is 0.06 to 0.1 μm and a minimum width of thewiring trench 25 is 0.06 μm. The wiring trench 25 and via hole 24 can beformed by dry etching using CF-containing etching gas and by using ahard mask constituted of, for example, two layers of an SiO film and anSiC film. The wiring trench 25 reaches the upper surface of the etchingstopper film 22, and the via hole 24 reaches the upper surface of thefirst layer wiring 11.

As shown in FIG. 3C, Mn is deposited by CVD on the upper surface of thewiring interlayer insulating film 23, the inner surface of the wiringtrench 25 and the inner surface of the via hole 24 to thereby form afirst film 32 having a thickness of about 2 nm. In the same chamber, Cuis deposited by CVD to form a second film 33. A preferred thickness ofthe second film 33 is determined by the size of a plan pattern of thevia hole 24. The “size of a plan pattern” means a diameter of a circleinscribed to the plan pattern of the via hole 24. For example, if theplan cross section of the via hole 24 is a circle, the size of the planpattern is the diameter of the circle, whereas if the plan cross sectionis a square, the size of the plan pattern is the length of one side ofthe square. In the following description, the size of the plan patternof the via hole is called “via diameter”. If the via diameter is 70 nm,a preferred thickness of the second film 23 is about 10 nm.

FIG. 4 is a schematic diagram of a CVD system. A substrate stage 101 isdisposed in a chamber 100. A vacuum pump 103 evacuates and exhausts theair in the chamber 100. A heater 102 is mounted in the substrate stage101. A semiconductor substrate 120 to be processed is held on the uppersurface of the substrate stage 101. A shower head 104 is disposed abovethe substrate stage 101.

Carrier gas, e.g., H₂ gas and liquid source material of Cu is suppliedto a carburetor 105. Trimethylvinylsilyl-hexafluoroacetylacetonatecopper (I) (hereinafter expressed as “Cu (hfac) tmvs) is used as Cusource material. Cu liquid source material is vaporized in thecarburetor 105 and supplied to a gas flow path 110 together with thecarrier gas.

Carrier gas, e.g., H₂ gas and Mn source material is supplied to a massflow controller (MFC) 106. Bismethylcyclopentadienyl manganese((CH₃C₅H₄)₂Mn) is used as Mn source material. Mn source material isvaporized in MFC 106 and supplied to a gas flow path 111 together withthe carrier gas. Purge gas, e.g., H₂ gas, is supplied to a gas flow path112.

The three gas flow paths 110, 111 and 112 become confluent at aconfluent point 115 and thereafter are connected to the shower head 104.Valves 116, 117 and 118 are inserted into the three gas flow paths 110,111 and 112, respectively. By controlling open/close of these valves 116to 118, desired gasses can be supplied to the shower head 104. Gassupplied to the shower head 104 is jetted out toward the semiconductorsubstrate 120 held on the substrate stage 101.

Description will be made on a method of forming the first film 32 andsecond film 33 shown in FIG. 3C. After the semiconductor substrate shownin FIG. 3B is placed on the substrate stage 101 heated in advance, theinside of the chamber 100 is evacuated. The valve 117 is opened tosupply Mn source material to the chamber 100. The film formingconditions are a substrate temperature of 100° C. to 300° C., typically200° C., an inner pressure of the chamber 100 of 0.3 Pa to 3 kPa,typically 500 Pa, an Mn source material flow rate of 0.2 g/min and acarrier gas flow rate of 500 sccm. When the first film of Mn having athickness of about 2 nm is formed, the valve 117 is closed and gasresident in the chamber 100 is exhausted.

Thereafter, the valve 116 is opened to supply Cu source material to thechamber 100. The film forming conditions are a substrate temperature of200° C., a pressure in the chamber 100 of 500 Pa, a Cu source materialflow rate of 1.0 g/min and a carrier gas flow rate of 500 sccm.

As shown in FIG. 3D, copper (Cu) is electroplated by using the secondfilm 33 as an electrode to form a conductive member 34. The wiringtrench 25 and via hole 24 are filled with the conductive member 34.Annealing is performed for about 5 minutes at a temperature of 300° C.to 400° C. in an atmosphere which contains a small amount of oxygen.

FIG. 3E is a cross sectional view of the substrate after annealing. Mnatoms in the first film 32 react with Si and O in the interlayerinsulating films 21 and 23 and etching stopper film 22 to form a barrierlayer 35 of MnSiO. Mn atoms, which diffused in the conductive member 34and reached the upper surface, react with oxygen. Therefore, a coverfilm 36 of manganese oxide is formed on the surface of the conductivemember 34. The first film 32 of Mn is merged with the barrier layer 35and extinguishes, and the second film 33 of Cu is merged with theconductive member 34.

As shown in FIG. 3F, an unnecessary conductive member 34 is removed bychemical mechanical polishing (CMP). The conductive member 34 left inthe wiring trench 25 and via hole 24 constitutes the second layer wiringand functions also as an interlayer connection member between the firstand second layer wirings. A portion of the hard mask used as an etchingmask when the wiring trench 25 shown in FIG. 3B is formed may be left onthe interlayer insulating film 23 to use this hard mask as a polishingstopper film of CMP.

In the first embodiment described above, the barrier layer 35 preventscopper diffusion and improves adhesion of the conductive member 34.Until the barrier layer 35 is formed, i.e., in the states shown in FIGS.3C and 3D, the first film 32 of Mn formed by CVD ensures sufficientadhesion to the underlying insulating film. Since the second film 33 ofCu is used as the electrode for electroplating, the electrode resistancecan be lowered compared to a conventional method using a CuMn alloy filmas the electrode. Since the second film 33 is formed by CVD, a thicknessof the second film 33 can be made more uniform than the case where thefilm is formed by sputtering.

In the first embodiment, although the first film 32 and second film 33are formed by CVD, these films may be formed by ALD which is a specificexample of CVD. If the first film 32 is to be formed by ALD, supply ofMn source material and purge in the chamber 100 by using purge gas arealternately repeated. If the second film 33 is to be formed by ALD,supply of Cu source material and purge in the chamber 100 by using purgegas are alternately repeated.

In the first embodiment, (CH₃C₅H₄)₂Mn is used as Mn source material.This source material has a vapor pressure of about 133 Pa (1 Torr) at atemperature of 85° C. to 90° C. If a cyclopenta group is wholly desorbedfrom Mn atoms, it is advantageous in that impurities are hard to bemixed in the first film 32. The cyclopenta group and Mn atoms arecoupled through π coupling. This π coupling is relatively weak couplingso that the cyclopenta group is easy to be desorbed from Mn atoms evenat a low temperature.

Mn source material having such advantages may includebisisopropylcyclopentadienyl manganese ((i-C₃H₇C₅H₄)₂Mn).(i-C₃H₇C₅H₄)₂Mn is liquid at an ordinary temperature and has a vaporpressure of 33.25 Pa (0.25 Torr) at a temperature of 87° C. to 88° C.

Next, description will be made on a semiconductor device manufacturemethod according to the second embodiment. In the first embodimentdescribed above, the second film 33 shown in FIG. 3C is formed by CVD.In the second embodiment, the second film 33 of Cu is formed bysputtering. The other processes are the same as those of thesemiconductor device manufacture method of the first embodiment. Whenthe second film 33 is to be formed by sputtering, a preferred thicknessof the second film 33 is 20 nm to 100 nm at a via diameter of 70 nm ofthe via hole 24. A film deposited on the inner surface of the via hole24 is thinner than a film deposited on a flat surface.

Since a method of forming a Cu film by sputtering is already use in amass production, the method has excellent process stability. Also in thesecond embodiment, since the first film 32 is formed by CVD, sufficientadhesion can be ensured between the first film 32 and underlyinginsulating film.

Next, description will be made on a semiconductor device manufacturemethod according to the third embodiment. In the third embodiment, thefirst film 32 shown in FIG. 3C is formed by sputtering using alloycontaining Cu and Mn as a target. The first film 32 is therefore made ofalloy containing Cu and Mn. The other processes are the same as those ofthe semiconductor device manufacture method of the first embodiment. Athickness of the first film 32 is 2 nm to 5 nm.

In the third embodiment, sufficient adhesion can be ensured between thefirst film 32 and underlying insulating film while the second film 33 isformed by CVD at a substrate temperature condition of 200° C. after thefirst film 32 shown in FIG. 3C is formed by sputtering.

Next, description will be made on a semiconductor device manufacturemethod according to the fourth embodiment. In the fourth embodiment, thefirst film 32 shown in FIG. 3C is formed by CVD and made of alloycontaining Cu and Mn. A thickness of the first film 32 is 2 nm to 5 nm.Similar to the second embodiment, the second film 33 is formed bysputtering. Similar to the first embodiment, the second film 33 may beformed by CVD.

In the following, with reference to FIG. 4, description will be made ona method of forming the first film 32 of alloy containing Cu and Mn byCVD. After the semiconductor substrate shown in FIG. 3B is placed on thesubstrate stage 101 heated in advance, the inside of the chamber 100 isevacuated. The valves 116 and 117 are opened to supply Cu and Mn sourcematerials to the chamber 100 at the same time. The film formingconditions are a substrate temperature of 100° C. to 300° C., typically200° C., an inner pressure of the chamber 100 of 0.3 Pa to 3 kPa,typically 500 Pa, an Mn source material flow rate of 0.2 g/min, a Cusource material flow rate of 1.0 g/min and a carrier gas flow rate of500 sccm.

The Cu source material and Mn source material used in the embodiment canrespectively deposit a Cu film and an Mn film at the same substratetemperature. Byproducts desorbed from Cu atoms and Mn atoms are stablesubstance. Therefore, side reaction is hard to occur between byproducts.Cu and Mn have similar electronegativities (Mn has an electronegativityof 1.5 and Cu has an electronegativity of 1.9). Side reaction istherefore hard to occur between Cu and compound desorbed from Mn andbetween Mn and compound desorbed from Cu. From these reasons, it ispossible to supply Cu source material and Mn source material at the sametime and deposit CuMn alloy.

The first film 32 may be formed by ALD which is a specific example ofCVD. When the first film 32 is to be formed by ALD, concurrent supply ofMn source material and Cu source material and purge in the chamber 100by using purge gas are alternately repeated.

Also in the fourth embodiment, since the first film 32 contains Mn, thebarrier layer 35 of MnSiO shown in FIG. 3E can be formed. Since thefirst film 32 is formed by CVD, sufficient adhesion can be ensuredbetween the first film 32 and underlying insulating film.

Next, with reference to FIGS. 5A to 5C, description will be made on asemiconductor device manufacture method according to the fifthembodiment.

The structure shown in FIG. 5A is the same as that of FIG. 3B referredto when the manufacture method of the first embodiment was described.

As shown in FIG. 5B, alloy containing Cu and Mn is deposited by CVD onthe upper surface of the wiring interlayer insulating film 23, the innersurface of the wiring trench 25 and the inner surface of the via hole 24to form an underlying film 40 having a thickness of about 5 nm to 50 nm.A method of forming the underlying film 40 is similar to that of formingthe first film 32 of the fourth embodiment. However, a ratio of thesupply amount of Mn to the supply amount of Cu is adjusted so that thetotal number of Mn atoms in the underlying film 40 is substantiallyequal to that of Mn atoms in the Mn film having a thickness of about 2nm.

As shown in FIG. 5C, Cu is electroplated by using the underlying film 40as an electrode to form a conductive member 34. Therefore, the wiringtrench 25 and via hole 24 are fully filled with the conductive member34. The subsequent processes are the same as those executed after theintermediate time shown in FIG. 3D.

In the fifth embodiment, since the underlying film 40 shown in FIG. 5Bis formed by CVD, sufficient adhesion can be ensured between theunderlying film 40 and underlying insulating film. As compared toforming the underlying film by sputtering, a thickness of the underlyingfilm 40 can be made generally uniform.

Next, description will be made on a semiconductor device manufacturemethod according to the sixth embodiment. Although Mn and Cu sourcematerials are supplied at the same time to form the underlying film 40shown in FIG. 5B in the fifth embodiment, two source materials aresupplied alternately in the sixth embodiment. The other processes arethe same as those of the manufacture method of the fifth embodiment.However, a ratio of the supply amount of Mn to the supply amount of Cuis adjusted so that the total number of Mn atoms in the underlying film40 is substantially equal to that of Mn atoms in the Mn film having athickness of about 2 nm. ALD may be adopted by which the supply ofsource material and the supply of purge gas are alternately repeatedduring the supply period of Mn source material and during the supplyperiod of Cu source material.

Also in the sixth embodiment, since the underlying film 40 is formed byCVD, similar effects to those of the fifth embodiment can be obtained.

Next, with reference to FIGS. 6A to 6C, description will be made on asemiconductor device manufacture method according to the seventhembodiment.

The structure shown in FIG. 6A is the same as that shown in FIG. 3Breferred to when the manufacture method of the first embodiment wasdescribed.

As shown in FIG. 6B, a first film 32 of Mn having a thickness of 2 nm isformed by CVD on the upper surface of the wiring interlayer insulatingfilm 23, the inner surface of the wiring trench 25 and the inner surfaceof the via hole 24. The first film 32 is formed by the same method asthat used for forming the first film 32 of the first embodiment shown inFIG. 3C.

As shown in FIG. 6C, Cu is deposited by CVD on the first film 32 to forma conductive member 34. Therefore, the wiring trench 25 and via hole 24are fully filled with the conductive member 34. The subsequent processesare the same as those executed after the intermediate time shown in FIG.3D.

In the seventh embodiment, since the first film 32 shown in FIG. 6B isformed by CVD, sufficient adhesion can be ensured between the first film32 and underlying insulating film. Further, since the conductive member34 is also formed by CVD, Cu can be deposited in the fine via hole andwiring trench with better reproductivity, as compared to electroplatingCu.

Cu may be deposited by CVD in a partial space in the via hole 24 andwiring trench 25 and the remaining space may be embedded byelectroplating.

Next, description will be made on a semiconductor device manufacturemethod according to the eighth embodiment. Although the first film 32shown in FIG. 6B is made of Mn in the seventh embodiment, the first filmof the eighth embodiment is made of alloy containing Cu and Mn. Thefirst film 32 is formed by CVD similar to that for the first film 32 ofthe fourth embodiment.

Also in the eighth embodiment, since the first film 32 is formed by CVD,similar effects to those of the seventh embodiment can be obtained.

Next, with reference to FIGS. 7A and 7B, description will be made on asemiconductor device manufacture method according to the ninthembodiment.

The structure shown in FIG. 7A is the same as that shown in FIG. 3Breferred to when the first embodiment manufacture method was described.

As shown in FIG. 7B, alloy containing Cu and Mn is deposited by CVD toembed CuMn alloy in the wiring trench 25 and via hole 24. A conductivemember 34 of CuMn alloy is therefore formed. Namely, it can beconsidered that the ninth embodiment is the same as a method ofcontinuing to form the first film 32 of the eighth embodiment shown inFIG. 6B until the via hole 24 and wiring trench 25 are fully filled withCuMn alloy. If it is difficult to fully fill the wiring trench 25 withCuMn alloy by using only CVD, CuMn alloy may be deposited by CVD andthen Cu may be electroplated supplementarily. The subsequent processesare the same as those executed after the intermediate time shown in FIG.3D.

For example, in depositing CuMn alloy by CVD, a supply amount of Mnsource material is set to 0.004 g/min and a supply amount of Cu sourcematerial is set to 1.0 g/min. Under these conditions, CuMn alloy isdeposited to a thickness of 500 nm. The total number of Mn atomscontained in the conductive member 34 is substantially equal to that ofMn atoms in the Mn film having a thickness of about 2 nm.

During annealing, Mn in the conductive member 34 is segregated on theinner surfaces of the via hole 24 and wiring trench 25 to form a barrierlayer of MnSiO. At the same time, a cover film 36 of manganese oxide orthe like is formed on the upper surface of the conductive member 34.

In the ninth embodiment, since the conductive member 34 itself is formedby CVD, sufficient adhesion of the conductive member 34 can be ensured.

The present invention has been described in connection with thepreferred embodiments. The invention is not limited only to the aboveembodiments. It will be apparent to those skilled in the art that othervarious modifications, improvements, combinations, and the like can bemade.

1. A semiconductor device manufacture method comprising steps of: (a1)forming a concave portion in an interlayer insulating film formed on asemiconductor substrate; (a2) forming a first film of Mn by CVD, thefirst film covering an inner surface of the concave portion and an uppersurface of the insulating film; (a3) depositing conductive materialessentially consisting of Cu on the first film to embed the conductivematerial in the concave portion; and (a4) annealing the semiconductorsubstrate.
 2. The semiconductor device manufacture method according toclaim 1, wherein the step (a3) comprises steps of: forming a second filmof Cu by CVD or sputtering, the second film covering a surface of thefirst film; and electroplating conductive material essentiallyconsisting of Cu, by using the second film as an electrode.
 3. Thesemiconductor device manufacture method according to claim 1, wherein inthe step (a3), the conductive material is embedded in the concaveportion by depositing the conductive material essentially consisting ofCu using CVD.
 4. A semiconductor device manufacture method comprisingsteps of: (b1) forming a concave portion in an interlayer insulatingfilm formed on a semiconductor substrate; (b2) forming a first filmcontaining Cu and Mn by CVD, the first film covering an inner surface ofthe concave portion and an upper surface of the insulating film; (b3)depositing conductive material essentially consisting of Cu on the firstfilm to embed the conductive material in the concave portion; and (b4)annealing the semiconductor substrate.
 5. The semiconductor devicemanufacture method according to claim 4, wherein in the step (b2), thefirst film is formed by supplying Cu source material and Mn sourcematerial at the same time.
 6. The semiconductor device manufacturemethod according to claim 4, wherein in the step (b2), the first film isformed by supplying Cu source material and Mn source materialalternately.
 7. The semiconductor device manufacture method according toclaim 4, wherein in the step (b3), the conductive material is embeddedin the concave portion by electroplating the conductive material usingthe first film as an electrode.
 8. The semiconductor device manufacturemethod according to claim 4, wherein in the step (b3), the conductivematerial containing Cu and Mn is embedded in the concave portion bycontinuing deposition of the first film by CVD in the step (b2).
 9. Thesemiconductor device manufacture method according to claim 4, whereinthe step (b3) comprises: forming a second film of Cu on the first filmby sputtering; and electroplating conductive material essentiallyconsisting of Cu by using the second film as an electrode.
 10. Asemiconductor device manufacture method comprising steps of: (c1)forming a concave portion in an interlayer insulating film formed on asemiconductor substrate; (c2) forming a first film containing Cu and Mnby sputtering, the first film covering an inner surface of the concaveportion and an upper surface of the insulating film; (c3) forming asecond film of conductive material essentially consisting of Cu by CVDon the first film; and (c4) embedding conductive material essentiallyconsisting of Cu in the concave portion.
 11. The semiconductor devicemanufacture method according to claim 10, wherein in the step (c4), theconductive material is electroplated by using the second film as anelectrode.
 12. A semiconductor device manufacture method of depositingalloy containing Cu and Mn on a semiconductor substrate by CVD while Mnsource material and Cu source material are supplied at the same time.13. The semiconductor device manufacture method according to claim 12,wherein bismethylcyclopentadienyl manganese orbisisopropylcyclopentadienyl manganese is used as the Mn sourcematerial.